Analyzing & Testing

Differential Scanning Calorimetry

Method, Technique, Applications

DSC 404 F1/F3

DSC 404 F1/F3 Pegasus Method

Differential Scanning Calorimetry

Differential scanning calorimetry
(DSC) is one of the most frequently
employed thermal analysis methods.
It can be used to analyze nearly any
energetic effect occurring in a solid or
liquid during thermal treatment.

DSC Analysis Possibilities

Specific heat capacity

Melting and crystallization behavior
Solid-solid transitions
Polymorphism
Phase transitions/diagrams
Liquid crystal transitions
Eutectic purity
Degree of crystallinity
Glass transition temperatures
Cross-linking reactions
Oxidative stability
Decomposition onset
Compatibility
Purity Determination
Thermokinetics

The DSC 404 F1/F3 Pegasus instruments meet nearly every respective
instrument and application standard,
including:
ISO 11357, ASTM E967, ASTM E968,
ASTM E793, ASTM D3895, ASTM
D3417, ASTM D3418, DIN 51004,
DIN 51007, DIN 53765.

Difference
~ Mass cp
TR

TM

TM

TS

t1

t2

T = TR - TS

The DSC 404 F1 and F3 Pegasus

systems operate according to the heat
flux principle. With this method, a
sample and a reference are subjected
to a controlled temperature program
(heating, cooling or isothermal). The
actual measured properties are the
temperature of the sample and the
temperature difference between
sample and reference. From the raw
data signals, the heat flow difference
between sample and reference can be
determined.

TC Voltage [V]
(~ Temperature)

DSC Method

Reference signal
Sample signal
Transition temperature

Time [s]

Area A
~ Transition enthalpy

Difference (from 0)
~ Mass cp

t1

t2

Time [s]

Signal generation in a heat flux DSC

DSC 404 F1/F3 Pegasus Outstanding Features

Pure Flexibility Furnace Variety for

the Broadest of Temperature Ranges
Various furnaces including those for
special applications extend the
application range beyond that of
common thermal analyzer systems.
Measurements can be performed in
the range from -150C to 2000C.

Double Hoist High Sample

Throughput
The double hoist allows for either the
simultaneous connection of two
furnaces or one furnace in combination with the automatic sample
changer (ASC).

Vacuum-Tight Design for

Elimination of Atmospheric
Influences
Mass flow controllers provide an ideal
means of testing materials sensitive to
oxidation. Enthalpy changes and the
specific heat (cp) can be analyzed at
unmatched levels of accuracy.

Pure Flexibility Sensor Variety

Efficient Time Management

The instruments ample flexibility is

extended by an impressive assortment
of sensors. The great variety of
possible furnace/sensor combinations
ensure an optimal configuration for
any application. Easy handling is
guaranteed by means of the userfriendly design.

The automatic sample changer (ASC)

is designed to handle up to 20
samples. Flexibility and high sample
throughput allow for efficient time
management.

Pure Flexibility Acessories for

Special Configurations
A variety of optional accessories and
special configurations are available to
ideally optimize the base system and
adjust it to specific needs.

Pure Flexibility in Groundbreaking Technology

Vacuum-Tight Design Optimum

Atmosphere Control
The DSC 404 F1/F3 Pegasus instruments stand out as first-rate vacuumtight high-temperature DSCs. Practically every component is constructed
to fulfill the requirements of highvacuum and high-purity gas applications. Various pump systems are
available to evacuate the system down

Atmosphere Mass Flow

Controllers
to 10-4 mbar. Automatic evacuation
is of course possible, as is backfilling
with various kinds of purge gases.
The OTS accessory can be used to
drastically reduce the oxygen
concentration at the sample to
below 1 ppm.

In the DSC 404 F3 Pegasus, the

purge or reactive gas flow is generally
controlled via frits, manual control
systems or tailor-made mass flow
control systems (MFCs). The DSC 404
F1 Pegasus comes standard-equipped
with integrated metal-housed mass
flow control systems for three different
gases.
Both MFC systems allow softwarecontrolled gas switching and purge
gas rates as well as recording of the
flow rates in the software.

gas outlet valve

gas outlet

thermocouple

hoisting device

heating element
sample carrier
protective tube
radiation shield
evacuating system
adjusting screws
purge 1
purge 2
protective

Various Furnace Systems

The DSC 404 F1/F3 Pegasus systems
can be equipped with a wide range of
different furnaces accommodating
different temperature and application
ranges between -150C and 2000C.
Silver and steel furnaces are available
for the sub-ambient temperature
range. Controlled cooling is guar-

Double Hoist
anteed with the liquid nitrogen
cooling device or the Vortex tube. For
higher temperature ranges, SiC, Pt, Rh
and graphite furnaces are available.
For working under humid atmospheres in combination with the
water-vapor furnace, a humidity
generator is available.

The electrically driven double furnace

hoist is a standard feature of the DSC
404 F1/F3 Pegasus systems. It allows
for simultaneous installation of two
different furnaces to conduct, for
example, low- and high-temperature
tests with the same instrument. For an
improved sample throughput, it is also
possible to connect a single furnace
along with the automatic sample
changer instead.

Interchangeable Furnaces
Type

Temperature Range

Cooling System

Atmospheres

-150C to 1000C

Liquid nitrogen/Vortex

Inert, oxidizing, reducing, vacuum, corrosive

Silver

-120C to 675C

Liquid nitrogen/Vortex

Inert, oxidizing, reducing, vacuum, corrosive

Water-vapor

RT to 1250C2

Air

Up to 100% humidity

Silicon carbide

RT to 1550C

Air

Inert, oxidizing, reducing, vacuum, corrosive

Platinum1

RT to 1500C

Air

Inert, oxidizing, reducing, vacuum

Rhodium

RT to 1650C

Air

Inert, oxidizing, reducing, vacuum

Graphite

RT to 2000C

Tap or chilled water3

Inert, oxidizing (with protective tube
(or cooling thermostat) up to 1750C ), reducing

Steel
1

Optimally suited for cp determination

Depending on the humidity content
3
Requires connection to cooling water
1
2

Pure Flexibility in Groundbreaking Technology

Various Sensors

Unique Sensor Adjustment System

The DSC 404 F1/F3 Pegasus instruments are generally used to obtain
accurate specific heat (cp) measurements. However, the systems allow for
simple DTA measurements or conventional DSC tests as well. DTA sensors
can be used for applications such as

routine tests on aggressive sample

substances. Various thermocouple
types allow optimum sensitivity and
time constants in all temperature
ranges. The sensors can easily be
changed in less than a minute by the
operator.

DTA sensor
with protected
thermocouples

For optimizing the baseline, a

micrometer adjustment system is
integrated into the measurement part.
This adjustment system allows
placement of the sensor at the
optimum central position in the
furnace. This guarantees a stable and
reproducible baseline without any
major adjustment efforts.

DSC sensor

DSC sensor in
round design

DSC sensor in
octagonal design
for ASC
operation

Interchangeable Sensors
Thermocouple

1
2

Temperature Range

Sensor Types

Atmospheres

DTA

DSC

DSC-cp

Inert

Oxidizing Reducing1 Vacuum

-150C to 700C

-160C to 800C

-150C to 1000C

RT to 1650C

SProtected

RT to 1650C

RT to 1750C

W/Re

RT to 2000C

Upper temperature limit may deviate from the maximum temperature range of the sensor
Optimum accuracy to 1500C

3
4

> 300C to max. 1200C

Up to 500C

Corros.

Technical Key Data of the DSC 404 F1/F3 Pegasus

DSC 404 F1 Pegasus
Temperature range

-150C to 2000C

Furnaces

Standard and special furnaces

Heating/cooling rate
Furnace hoist

0.001 K/min to 50 K/min (depending on furnace type)

Motorized double hoist for two furnaces or one furnace combined with the ASC

Sensor types
cp measuring range

DSC 404 F3 Pegasus

DTA, DSC, DSC-cp, quick and safe interchange

Up to 5 J/(g*K)

cp determination1

Yes

Optional

TM-DSC

Yes

No

BeFlat (DSC)

Yes

Optional

Tau-R Mode

Yes

Optional

Optional

Optional

Yes

Optional

Purity Determination
Macro recorder for analysis routines
Gas atmospheres

Inert, oxidizing, reducing, vacuum (10-4 mbar)

Vacuum-tightness

10-4 mbar (10-2 Pa)

Gas control
Automatic sample changer (ASC)
Automatic evacuation
Coupling to evolved gas analyzers
PulseTA

3 integrated mass flow

controllers (MFC)

3 integrated frits optionally

3 mass flow controllers (MFC)

20 samples, removable carousel

Software-controlled

Optional

FT-IR, MS, FT-IR-MS, GC-MS, GC-MS-FT-IR

Optional

cp, specific heat capacity

A Diverse Array of Accessories

Plethora of Crucibles

Automatic Sample Changer (ASC)

Remove Lid Function of the ASC

What sets the DSC 404 F1/F3

Pegasus systems apart is not only
their flexibility in furnaces and sensors
but also the huge variety of available
crucibles. For the broad temperature
range from -150C to 2000C, the
crucible materials vary from metals (Al,
Ag, Au, etc.) to ceramics (Al2O3, MgO,
ZrO2, Y2O3, BN, etc.) to graphite. For
inhomogeneous samples and those
with low density, larger crucibles are
available.

An automatic sample changer (ASC)

can be installed on both the DSC 404
F1 and F3 Pegasus systems. The
sample carousel allows for 20 samples
and is removable for easy loading.
Each sample can be assigned an
individual measurement and evaluation macro. Preprogramming permits
measurements to be carried out
overnight or on weekends. This
significantly enhances the sample
throughput, laboratory and
instrument efficiency.

For unstable samples i.e., samples

sensitive to oxygen or ambient room
conditions while waiting their turn on
the crucible magazine to be inserted
into the sample compartment a
remove lid device can be ordered
with the instrument. Closing the
crucibles with a lid minimizes the risk
that critical samples would evaporate
or react with ambient humidity prior
to the measurement.

Should samples need to be shut off

from the influence of the ambient
atmosphere, or should gas emissions
from the samples need to be contained,
aluminum crucibles can be sealed shut,
gas-tight, with a handy sealing press.
For measurements under increased
pressures of up to 100 bar, reusable
stainless steel and titanium autoclave
crucibles handle the job. A PtRh/
ceramic crucible system for measurements on metal melts or other reactive
test materials is available with a
removable liner. Liners are available
made of thin-walled Al2O3, MgO, and
Y2O3.

Reshaping tool for PtRh/ceramic crucbile system

10

Optimum crucible placement is

guaranteed by design. The ASC with
its gripper and carousel allows for the
use of nearly any crucible type
including specialties such as low-,
medium- and high-pressure crucibles.

Selection of DSC crucibles

AutoVac, OTS, Evacuation Systems

Glove Box and Corrosion-Resistant
Instrument Versions
A variety of useful accessories for
augmenting the application range of
the DSC method are available, including evacuation devices (from rotary or
diaphragm to turbo molecular
pumps), the AutoVac for automatic
evacuation and refilling of the DSC
system, and the OTS oxygen trap
system. In addition, special DSC versions are available for use in a glove
box and for measurements in corrosive
atmospheres. This great flexibility
allows the DSC 404 F1/F3 Pegasus
systems to be optimized and configured according to your needs
both now and in the future.

Getter material ring

Getter support

Radiation shield

DSC Sensor the OTS device removes traces of residual

oxygen in the gas atmosphere inside the instrument

Calibration Materials

For the calibration of temperature,

enthalpy and specific heat in both the
low- and high-temperature range,
multiple sets containing different
calibration materials are available for
the various crucible materials (including high-pressure autoclaves).

The calibration materials are selected

and prepared for measurement in
accordance with the recommendations of the corresponding ASTM and
CEI-IEC standards.

11

Proteus Software Key Features

Both DSC systems run under the Proteus software on Windows XP Professional,
or on Windows 7 32-/64-bit Professional, Enterprise or Ultimate. The Proteus
software includes everything you need to carry out a measurement and evaluate
the resulting data. User-friendly menus combined with automated routines make
this very easy to use while still providing sophisticated analysis. The Proteus
software is licensed with the instrument and can of course be installed on other
computer systems.

Key Features of the

General Software

Mulittasking: simultaneous
measurement and evaluation
Multimodeling: operation of
different instruments with one
computer
Automatic detection of instrument
settings (e.g., furnace, sensor, etc.)
Storage of the analysis results and
status for later restoration and
continuation with analysis (original
file remains)
Results by e-mail
Gas manager and gas control
segment by segment
Contextsensitive help system
Presentation of DSC curve in
absolute (V, mW) or relative
(V/mg, mW/mg) units
Calibration and correction routines
for temperature, sensitivity,
baseline
Export of graphics with evaluation
results to clipboard or to common
formats such as EMF, PNG, BMP,
JPG, TIF or PDF

12

Data export in Excel-compatible

CSV-format
ASCII file export of the raw data
and/or the corrected measurement
data for further data processing
Multiple-window technique for
clear presentation and evaluation
of measurement curves or graphical
excerpts in multiple windows
Formatting of the results, measurement values, and axis labels
optionally in technical format or
as scientific notation
Application languages: English,
German, French, Russian, Chinese
Print languages: English, German,
French, Russian, Chinese, Italian,
Spanish, Portuguese, Polish
Software produced by ISOcertified
company

Key Features of the

Measurement Software

Up to 256 programmable
temperature segments
Repetitive measurements with
minimum parameter input
Monitoring of all MFC gas flows
Loop programming: insertion,
deletion, and annexation of
temperature segments, even in
already existing temperature
programs
Snapshot for online evaluation of
the measurement in progress
Macro recorder for fully automatic
analysis
Special functions:
Jump to the next segment
Changing of upcoming segments
during measurement
OIT (softwarecontrolled
optimization of measuring time:
reset or jump to cooling segment)
TMDSC (only DSC 404 F1 Pegasus)
Instrument Cockpit App:
information on the current
measurement status, direct access
to the running test, ability to stop
the measurement remotely anytime

Key Features of the

Analysis Software

Comparison analysis of up to 64
curves/temperature segments from
the same or different measurements
Simultaneous analysis of multiple
curves
Loading of single files and simultaneous loading of multiple files
(curve and parameter preview)
Smoothing of the DSC curves with
adjustable filter factors
Calculation and presentation of the
first and second derivative
Value determination on a single
curve or a curve family
Curve subtraction of baselines
and sample runs; subtraction of
physically identical curves (DSC)
Shifting of freely selectable segments to the origin (zero point) on
the time axis to simplify comparison
between multiple heating (or
cooling) segments
Reimport of measurements saved
as ASCIIfiles

Connection of segments by spline

interpolation: Dynamic segments
with the same heating direction
and isothermal segments can
be analyzed as interrelated and
depicted temperaturescaled
Import of standard tables of specific
heat, freely configurable
Storage of the analysis results and
status for later restoration and
continuation with analysis
PIP graphical function (picture in
picture), exchange of the full curve
and excerpt graphics (FLIP) with
further results evaluation
Semiautomatic routines for the
determination of characteristic
temperatures (extrapolated onset,
point of inflection, peak maximum,
peak end)
Fully automatic routine for complex
peak evaluation (onset, point of
inflection, peak, end point, peak
height, peak width and peak area);
calculation according to DIN or ISO
method

Determination of peak areas and

partial peak areas using different
baselines (linear, areaproportional,
etc.)
Determination of the specific heat
cp(T), optionally also in accordance
with the ASTM method
Integration of the cp(T) curve for
determination of the enthalpy of a
reaction
Evaluation routine for glass
transition
OIT evaluation
Determination of the DSC integral
using the curve of the partial peak
areas (LF liquid fraction, solid fat
index)
Determination of the DSC
conversion curve in % using the
curve of the partial peak areas
based on the enthalpy of a
selectable reference substance
Determination of the temperaturedependent crystallinity curve from
partial peak areas and based on the
enthalpy of a selectable reference
substance

13

Proteus Software Modules and Expert Software Solutions

The Proteus modules and expert software solutions offer further advanced
processing of the thermoanalytical data for more sophisticated analyses. The
advanced software packages Peak Separation, Purity Determination and Thermokinetics are optionally available for both DSC versions. The Proteus software
extensions TauR Mode, BeFlat and Specific Heat Determination are optionally
available for the DSC 404 F3 Pegasus. TM-DSC is exclusively available for the
DSC 404 F1 Pegasus.

Tau-R Mode

DSC /mW
12

exo

The DSC curve not only incorporates

important information about the
sample, but also residual information
from the instrument. To correct for this
established fact, the TauR Mode has
been developed. This method is based
on two essential correction factors: the
thermal resistance (R) and the time
constant (). Determination and
creation of a correction file must be
carried out only once for identical
measurement parameters. The true
raw data can then be accessed by just
one click of the mouse.

10

Tau-R Mode
6

without Tau-R Mode

2

0
150

152

154

156

158

160

162

164

166

Temperature /C

Correction of the thermal resistance and the time constant lead to defined peaks (TauR Mode)

BeFlat
Perfect thermal symmetry, which
is often expected in a differential
measurement setup, is virtually
impossible to realize in practice. The
unique BeFlat software corrects
DSC baseline discrepancies attributable to thermal asymmetry by
using a multidimensional polynomial

14

dependent upon temperature and

heating rate. BeFlat removes the
baseline discrepancies from the DSC
signal and yields perfect horizontal
DSC baselines with minimal deviations in the W range. The true raw
data signal can be re-accessed at any
time with a simple click of the mouse.

Peak Separation

Specific Heat Determination

The Peak Separation software allows

for the mathematical separation of
overlapped peaks using profiles from
the following peak types: Gaussian,
Cauchy, pseudo-Voigt (linear combination of Gaussian and Cauchy),
Frazer-Suzuki (asymmetric Gaussian),
modified La-Place (double-sided
rounded) and Pearson. The software
fits the experimental data as an
additive superposition of peaks.

The specific heat capacity (cp) is an

important temperature-dependent
thermophysical property of a material.
The DSC method allows for convenient and reliable determination of
cp. Knowledge of the specific heat
capacity supports the improvement
and development of many technical
and technological processes, as well
as that of a broad variety of materials
from building materials to turbine
plates. This software module is based
on standardized methods described in
standards such as ASTM E1269,
ISO 11357, DIN 51007.

Purity Determination
Temp / C

The Purity Determination program is

applied to determine the purity of a
material by analyzing the DSC melting
peak. The calculation is carried out
using the Van t Hoff equation and is
based on the fact that the melting
process shifts to lower temperatures
and the DSC melting peaks broaden as
the impurity content increases. A given
application range could thus be
extended, for example, beyond an
impurity threshold of 5 mol% to an
estimated upper boundary of
10mol%. In addition, the thermal
resistance is adjusted so as to calculate
the nominal value for substances with
a known degree of purity.

133.5
133.4
133.3
133.2
133.1
133.0
132.9
132.8
132.7

++ +++
++ ++
++ ++
++ +++
++
++
++
++
[1.2]041-3-04-03.sd3
++
++
++
++
+
Van`t Hoff
+
+
++
++
+ Lin. Van`t Hoff
++
++
Line
+
++
++
++
++
+
++
++
++
++
++
++
++
++
++
++
++
++
++
Substance: Phenacetin
++
++
++
Molar mass: 179.220 g/mol
++
+
Purity: 97.965 %
++
++
++
Impurities: 2.035 %
++
++
++
T melting: 133.874 C
++
+++
+
T melting pure: 134.868 C
++
+++
Correction for linearization: 16.679 %
++
+++
Baseline: I
++
+++ [1++ [1.2]
++
1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

1/Partial Area

Purity results for phenacetin standard with a 2% aminobenzoic acid content

15

Proteus Software Modules and Expert Software Solutions

Temperature-Modulated DSC
Temperature-modulated DSC
(TM-DSC) is a DSC technique whereby
a sample is subjected to a superposition of a linear and a periodic
temperature program. Temperature-modulated DSC enables the
separation of overlapped DSC effects
by calculating the reversing and
non-reversing signals. Glass transitions can therefore be well separated
from, for example, exothermal
curing, decomposition, evaporation,
relaxation or cold-crystallization
processes in a single TM-DSC test.

The DSC 404 F1 Pegasus is the only

DSC which allows for TM-DSC tests
up to 1650C. Nearly all available
furnaces in combination with
different DSC sensors are suited for
such tests. The NETZSCH TM-DSC
technique is totally based on a
software solution. The advantages
can be summarized as follows:

Offline evaluation after the measurement. This means there is no

time delay of evaluated data, which
is common for online evaluations
FRC method which takes into
account the dependence of the
calibration coefficient on frequency,
thermal resistance between the
sample and crucible, and heat
capacity of the sample.

DSC /(mW/mg)
[non-reversing]
exo
0.04

0.02

Onset:
Mid:
End:
Delta Cp*:

glass transition

50.1 C
60.4 C
70.1 C
0.314 J/(g*K)

0.00
Area: -55.86 J/g
Peak*: 116.1 C

-0.02

-0.04

-0.06

Onset:
Mid:
End:
Delta Cp*:

curing process

48.0 C
55.9 C
62.3 C
0.235 J/(g*K)

-0.08
DSC (reversing)
DSC (non-reversing)
DSC (total)

-0.10

-0.12
40

60

80

100
120
Temperature /C

140

160

Curing of an unsaturated polyester resin and overlapping of an endothermal glass transition

can be separated in a single TM-DSC test.

16

180

This results in unique features which

do not all require calibration with a
cp standard. These include:

Unique baseline correction

algorithm for average, amplitude
and phase of the DSC curve
Standard DSC calibrations (using
melting points according to DIN
51007 and ASTM E967 or ASTM
E968)
Unique method of determination
of the calibration coefficients for
calculation of the reversing heat
capacity (cp standard required).

The NETZSCH TM-DSC solution improves separation of time-dependent

events from the total heat flow. It
supports the investigations of glass
transition, vitrification, crystallization,
evaporation, chemical reaction (e.g.,
curing), polymorphism and dehydration.

Thermokinetics
The Thermokinetics software module
is used to create kinetic models of
chemical processes based on a series
of laboratory tests under different
temperature conditions. It can also
be used to predict the behavior of
chemical systems under user-defined
conditions for process optimization.
Thermokinetics is capable of analyzing
any process with a reaction rate which
is a function of temperature and time.

The program contains the following

kinetic analysis and prediction
methods:

Model-free kinetic analysis

(Friedman, Ozawa-Flynn-Wall,
ASTM E698, ASTM E1641)
Model-fit using multivariate
nonlinear regression (model
definition, up to 6 multiple-step
reactions, 18 different reaction
types, F-test for fit quality and
significance of an additional step)

Analysis with Thermokinetics makes it

possible to determine the number of
reaction steps and the following
values for each step:

Reaction type
Activation energy
Reaction order
Other kinetic parameters

Heat flow rate (W/g)

Final Product / %

Final product vs time

Temperature / C

DSC - Kinetic Model

160

100

180C
Prediction

5 K/min
H -436.8 J/g

140
80

0.5

Partial Area /%
100

160C

80

140C

120

-1.0

-1.5

60

60

10 K/min
H -432.7 J/g

100

80

40

120C

40

60

-2.0

-2.5

20

step 1: nn order
step 2: 1n order
with autocatalysis by C
step 3: nn order

20

20 K/min
H -382.3 J/g

40

100C
0

50

100

150
200
Temperature / C

250

Fitting of the DSC curves by using the 3-step

reaction model

300

20
0

10

20
Time / min

30

40

Prediction for the final product according to a

temperature program

0
0

Time / min

12

16

20

The fractional reaction is calculated for a set of

temperatures and a certain time

17

Performance and Applications Specific Heat Capacity,

Phase Transitions

Accuracy of the Specific Heat Capacity of Alumina (Al2O3)

Presented in the figure is a specific
heat capacity test result for a polycrystalline alumina sample between
room temperature and 1600C.
Additionally shown are literature
values for pure alumina. There are
no significant differences between
the literature values and the test
results. The maximum deviations
are in the range of 2%, which
demonstrates the outstanding performance of the DSC 404 F1 Pegasus.

Cp /(J/(g*K))

1.4

Literature
Measured

1.2

1.0

0.8

0.6
200

400

600

800
1000
Temperature /C

1200

1400

1600

Highly accurate determination of the specific heat capacity across a wide temperature range.
For these measurements, the rhodium furnace and the DSC-cp sensor type S were used.

Determination of the Specific Heat Capacity of Molybdenum in the Low-Temperature Range

The specific heat of molybdenum
was measured three times between
-100C and 300C using the low-temperature furnace. The three results
(colored lines) are identical to within 2%. Additionally shown are literature values for pure molybdenum
(black line). The differences between
the measurement results and the
literature values are generally less
than 2%. This proves the excellent
specific heat performance of the
system in the low-temperature range.

Cp /(J/(g*K))

0.30

0.25

0.20

0.15

0.10
-100

-50

50

100
150
Temperature /C

200

250

300

The specific heat capacity in the sub-ambient temperature range can be determined up to 300C by
means of the steel furnace (-150C to 1000C) and the DSC-cp sensor type E.

18

Reproducibility of the Apparent Specific Heat

of a Diopside Glass Powder
Cp /(J/(g*K))
In this plot, the glass transition of
the powder occurred at 734C
(midpoint). Crystallization was measured at 883C (extrapolated onset).
Melting took place at 1390C (main
peak temperature). The characteristic temperatures and the corresponding enthalpy changes are in good
agreement between the two different samples. The specific heat itself
doesnt show relevant differences,
which indicates the excellent stability
and reproducibility of the DSC system.

40
Cp /(J/(g*K))
1390.3 C

30
40

1390.5 C

20
30

Onset:
723.5 C
Mid:
733.6 C
Inflection: 741.0 C
Onset:
723.8 C
End:
744.8 C
Mid:
733.9 C
Delta Cp*: 723.5
0.529
Inflection: 739.5 C
Onset:
C J/(g*K)
End:
744.9 C
Mid:
733.6 C883.4 C
Delta
Cp*:
0.522
J/(g*K)
Inflection: 741.0 C 883.2 C
Onset:
723.8 C
End:
744.8 C
Mid:
733.9 C
Delta Cp*: 0.529 J/(g*K)
Inflection: 739.5 C
End:
744.9 C
883.4 C
Delta Cp*: 0.522 J/(g*K)
883.2 C
908.1 C
908.0 C

10
20
0
10
-10
0
-20
-10

1390.3 C
1390.5 C

1055.0 C
1055.0 C

1055.0 C
1055.0 C

908.1 C

200

400

600
800 908.0 C1000
Temperature /C

1200

1400

200

400

600
800
Temperature /C

1200

1400

-20
1000

Excellent reproducibility and the detection of weak phase transitions (glass transition) can be achieved
by simply combining the right furnace with the right sensor. These DSC runs were carried out with the
Pt furnace and by using DSC-cp sensor type S.

Phase Transitions of Iron

The specific heat flow rate of iron was
here measured between room temperature and 1620C. The peak at 770C
is due to a change in the magnetic
properties of the material (the Curie
transition). At peak temperatures of
926C and 1399C, two changes in
the crystal structure occurred. Most
likely due to impurities in the material, these temperatures are slightly
shifted from the literature values
[1] for pure iron. Melting occurred
at 1534C (extrapolated onset). The
heat of fusion was 266.1 J/g. This is
less than a 1.5% deviation from typical literature values for pure iron.
[1] Das Techniker Handbuch, Grundlagen und
Anwendungen der Maschinenbau-Technik,
15. Auflage, Herausgeber Alfred Bge, Vieweg
Verlag, 1999

DSC /(mW/mg)

exo

7
DSC /(mW/mg)
6 exo
7
5
6
4
5
3
4
2
3
1
2
0
1
-1
200
0

1559.7 C

1559.7 C

266.1 J/g

1399.3 C
266.1 J/g

926.4 C
770.2 C

16.13 J/g

16 J/g

1399.3 C

926.4 C
770.2 C

400

600

16 J/g

800
1000
Temperature /C

1534.0 C

16.13 J/g

1200

1400

1534.01600
C

-1
200
400
600
800
1000
1200
1400
1600
Sharp peaks, reliable peak areas and a stable baseline
over a broad
temperature range are the
Temperature
/C
dominant attributes of results produced by the DSC 404 F3 Pegasus system equipped with the
rhodium furnace.

19

Performance and Applications TMDSC, Melting and

Crystallization

Temperature-Modulated DSC (TM-DSC) Measurement on a Ceramic Glass

For TMDSC, the heating rates are
varied by overlapping the underlying
linear heating rates with a sinusoidal temperature modulation. At the
same time, the sample is subjected to a
nonlinear temperature change which
is relatively fast in comparison with
the linear rate. These two conditions
lead to the benefit of temperaturemodulated DSC measurements: separation of reversing (thermodynamic) and
non-reversing (kinetic) thermal effects.
As shown with the example of a ceramic glass, the modulated signal (blue
curve) is separated in a reversing (red
curve) and nonreversing (green curve)
signal. The reversible energetic effect
can be seen from the reversing curve.
Here, the glass transition was detected at 788C. The relaxation peak was
detected at 769C in the total signal
(blue curve) and especially in the
non-reversing curve (green). Recrystallization and melting were observed
as non-reversing signals at peak temperatures of 1030C and 1158C.
These results demonstrate that
reversible and nonreversible effects
which may overlap in case of glass
transitions and relaxation effects
can be separated by TMDSC.
The nonreversing signal appears
very similar to the total heat flow.
It can be taken for kinetic studies
and evaluation of the relaxation
enthalpy and peak temperature.

DSC /(mW/mg)
DSC /(mW/mg)
0.6 exo
0.6 exo
0.5
0.5

DSC /(mW/mg)
exo
DSC /(mW/mg)
0,18
exo
0,18
0,16

0.4
0.4

0,16
0,14
0,14
0,12
0,12
0,10

0.3
0.3

0,10
0,08
0,08
0,06
0,06
0,04

0.2
0.2

0,04

700

710

720

730

740
750
Temperature /C

760

770

780

790

700

710

720

730

740
750
Temperature /C

760

770

780

790

0.1
0.1
0.0
0.0
-0.1
-0.1

300
300

400
400

500
500

600
600

700
800
Temperature
/C
700
800
Temperature /C

900
900

1000
1000

1100
1100

1200
1200

The simplest evaluation of a typical TMDSC measurement is the determination of the total heatflow
curve as an average value of the modulated heatflow differential curve. Modulated signal (light blue
curve) and average values (dark blue curve: total heat flow).

DSC /(mW/mg)
DSC /(mW/mg)
[total]
exo
[total]
exo
0.3
0.3

1147 C 1158 C
1147 C 1158 C

DSC (reversing)
(reversing)
DSC DSC
(non-reversing)
DSC (non-reversing)
DSC (total)
DSC (total)

0.2
0.2

769 C
769 C

0.1
0.1

852 C 884 C
852 C 884 C

-129.2 J/g
-129.2 J/g

6.077 J/g
6.077 J/g

0.0
0.0

1033 C
1033 C
Mid:
788 C
Mid: Cp*: 0.234
788 CJ/(g*K)
Delta
Delta Cp*: 0.234 J/(g*K)
853 C 878 C
768 C
853 C 878 C
768 C

-0.1
-0.1
-0.2
-0.2

10.64 J/g
10.64 J/g

-0.3
-0.3

1196 C
1196 C
247.1 J/g
247.1 J/g
1147 C 1158 C
1147 C 1158 C

1195 C
1195 C

-130.6 J/g
-130.6 J/g

7.3 J/g
7.3 J/g

237.6 J/g
237.6 J/g
1025 C
1025 C

600
600

700
700

800
800

900
Temperature
/C
900
Temperature /C

1000
1000

1100
1100

1200
1200

The TMDSC measurement was carried out in a synthetic air atmosphere at a heating rate of 3 K/min
and amplitude of 0.5 K/min for a period of 60 s. Highplatinum crucibles with pierced lid were used.
The sample mass amounted to 45 mg.

20

Melting and Crystallization of AlCuMg

The DSC 404 F1/F3 Pegasus systems are able to perform controlled
cooling runs. Here, the heating (blue
curve) and cooling (green curve) runs
on an AlCuMg alloy are presented.
Melting occurs at 646C (peak). Up
to 800C, no further thermal effects
can be observed. Subsequent cooling
leads to crystallization of the alloy.
After a minor supercooling effect,
crystallization reaches its maximum
at 618C. The melting and crystallization enthalpy are nearly identical.
However, the shoulder in the crystallization peak already indicates crystallization of more than one structure.

DSC /(mW/mg)

exo
3
DSC /(mW/mg)
2

646 C

exo

3
646 C

1
2

360.3 J/g

475 C

-359.2 J/g
506 C

1
-1

360.3 J/g

475 C

-359.2 J/g
506 C

-2
-1

618 C

-3
-2 300

400

500

600
Temperature /C

700

800

618 C

-3 with a Al O liner were used in order to prevent chemical reactions between the melt and
Pt crucibles
2 3
the crucible300
material during400
a DSC measurement.
Oxidation600
was avoided by 700
using an argon atmosphere.
500
800
Temperature /C

Melting Point Determination at Highest Temperatures

DTA /(V/mg)
Determination of the melting and
crystallization temperature up to
2000C becomes possible by using
the appropriate DTA sensor (type
W/Re) and the graphite furnace. This
example shows the heating (black
curve) and cooling (green curve) runs
on a vanadium sample (99.7 %).
The DTA crucibles made of ZrO2 are
suitable in the highest temperature
range. Melting occurs at an extrapolated onset temperature of 1887C.
During cooling, the sample recrystallizes with only a small supercooling
effect at 1877C (peak).

[1.2]
exo

Peak: 1906.2 C

1.0
DTA /(V/mg)
0.5[1.2]
exo

Onset: 1886.6 C

1.0
0.0
0.5
-0.5

Peak: 1906.2 C

End: 1882.5 C
Onset: 1886.6 C

0.0
-1.0
End: 1882.5 C

-0.5
-1.5

Peak: 1876.8 C

-1.0
1700

1750

1800

-1.5

1850
Temperature /C

1900

1950

2000

1900

1950

2000

Peak: 1876.8 C

1700

1750

1800

1850
Temperature /C

DTA measurement on vanadium in crucibles made of zirconium oxide (ZrO2); heating rate 20 K/min,
cooling 75 K/min helium atmosphere.

21

Expertise in Service

Our Expertise Service

All over the world, the name NETZSCH
stands for comprehensive support and
expert, reliable service, before and
after sale. Our qualified personnel
from the technical service and
application departments are always
available for consultation.
In special training programs tailored
for you and your employees, you will
learn to tap the full potential of your
instrument.
To maintain and protect your
investment, you will be accompanied
by our experienced service team over
the entire life span of your instrument.

22

Summary of Our Services

Installation and commissioning

Hotline service
Preventive maintenance
Calibration service
IQ /OQ/PQ
On-site repairs with emergency
service for NETZSCHcomponents
Moving/exchange service
Technical information service
Spare parts assistance

Our Expertise Applications Laboratories

The NETZSCH Thermal Analysis
applications laboratories are a
proficient partner for nearly any
Thermal Analysis issue. Our
involvement in your projects begins
with proper sample preparation and
continues through meticulous
examination and interpretation of the
measurement results. Our diverse
methods and over 30 different
state-of-the-art measuring stations
will provide ready-made solutions for
all your thermal needs.
Within the realm of thermal analysis
and the measurement of thermophysical properties, we offer you a
comprehensive line of the most
diverse analysis techniques for
materials characterization (solids,
powders and liquids).

Measurements can be carried out on

samples of the most varied of geometries and configurations. You will
receive high-precision measurement
results and valuable interpretations
from us in the shortest possible time.
This will enable you to precisely
characterize new materials and
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deployment, minimize risks of failure,
and gain decisive advantages over
your competitors.
For production problems, we can work
with you to analyze concerns and
develop solutions. The minimal
investment in our testing and services
will reward you with reduced down
time and reject rates, helping you
optimize your processes across the
board.

23

The NETZSCH Group is a mid-sized, family-owned German company engaging in

the manufacture of machinery and instrumentation with worldwide production,
sales, and service branches.
The three Business Units Analyzing & Testing, Grinding & Dispersing and
Pumps & Systems provide tailored solutions for highest-level needs. Over
3,000 employees at 163 sales and production centers in 28 countries across
the globe guarantee that expert service is never far from our customers.

www.netzsch.com/n26127

NETZSCH-Gertebau GmbH
Wittelsbacherstrae 42
95100 Selb
Germany
Tel.: +49 9287 881-0
Fax: +49 9287 881 505
at@netzsch.com

NGB DSC 404 F1/F3 Pegasus EN 500 06/13 LH Technical specifications are subject to change.

When it comes to Thermal Analysis, Adiabatic Reaction Calorimetry and

the determination of Thermophysical Properties, NETZSCH has it covered.
Our 50 years of applications experience, broad state-of-the-art product line
and comprehensive service offerings ensure that our solutions will not only
meet your every requirement but also exceed your every expectation.